EP0362814B1 - Copolymer von Ethylen und ein polycyclisches Monomer, Verfahren zu deren Herstellung und optischer Artikel - Google Patents

Copolymer von Ethylen und ein polycyclisches Monomer, Verfahren zu deren Herstellung und optischer Artikel Download PDF

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EP0362814B1
EP0362814B1 EP89118391A EP89118391A EP0362814B1 EP 0362814 B1 EP0362814 B1 EP 0362814B1 EP 89118391 A EP89118391 A EP 89118391A EP 89118391 A EP89118391 A EP 89118391A EP 0362814 B1 EP0362814 B1 EP 0362814B1
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general formula
ethylene
represented
random copolymer
units derived
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EP0362814A2 (de
EP0362814A3 (de
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Yasuaki Showa Denko K.K. Oita Sasaki
Tohru Showa Denko K.K. Oita Matsuoka
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Resonac Holdings Corp
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Showa Denko KK
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Priority claimed from JP25080588A external-priority patent/JP2668414B2/ja
Priority claimed from JP14990789A external-priority patent/JPH0314805A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • the present invention relates to an ethylene/polycyclic monomer random copolymer, a process for the preparation of this random copolymer, and an optical article formed by molding this random copolymer.
  • This random copolymer has an excellent transparency, is optically homogeneous, has a small birefringence, and a well-balanced heat resistance, chemical resistance, dimensional stability, rigidity and other mechanical properties.
  • This copolymer is valuable for use in the manufacture of an optical disk, an optical fiber, an optical filter, a plastic lens and the like.
  • a polycarbonate resin and a polymethyl methacrylate resin are mainly used as the material of an optical disk substrate.
  • the polycarbonate resin has a high glass transition temperature (Tg), and thus the polycarbonate resin has a high heat resistance, good transparency, dimensional stability, and mechanical properties. Nevertheless, since the hygroscopicity of the polycarbonate resin is relatively high and the birefringence is large, the optical anisotropy of the polycarbonate resin is large. Furthermore, the polycarbonate resin has low resistance to an alkali, and the polycarbonate resin tends to undergo hydrolysis.
  • the polymethyl methacrylate resin has excellent optical properties, for example, the polymethyl methacrylate resin has a high transparency and a small birefringence. Moreover, the polymethyl methacrylate has good mechanical properties. However, since the hygroscopicity of the polymethyl methacrylate resin is high, a substrate formed of this resin is easily corroded, and warping often occurs in the disk surface owing to a change of the dimension or shape. Furthermore, since the glass transition temperature (Tg) of the polymethyl methacrylate is about 100°C, distortion at a high temperature cannot be neglected. Still further, the polymethyl methacrylate has a poor solvent resistance.
  • Tg glass transition temperature
  • EP-A-0 203 799 and EP-A-0 283 164 provide random copolymers derived from ethylene or ⁇ -olefins and cycloolefin monomers, comprising six-membered bridged rings. In the compounds used therein the six-membered bridged rings are fused together, thereby exhibiting a structure in principle identical with cyclopentadiene, wherein predominantly the endo isomer is found.
  • a resin material having well-balanced transparency, optical properties, heat resistance, chemical resistance, dimensional stability and mechanical properties has not heretofore been known.
  • an object of the present invention is to provide a resin material which has an excellent transparency, is optically homogenous and has a small birefringence, and has well balanced heat resistance, chemical resistance, dimensional stability and mechanical properties.
  • a random copolymer which comprises recurring units derived from ethylene and recurring units derived from a polycyclic monomer represented by the following general formula (I): wherein l, m and n are 0 or 1, p is O or an integer of at least 1, R1 , R2 , R3 and R4 , which may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R3 and R4 may together form a ring; the molar ratio of ethylene/polycyclic monomer of the general formula (I) being in the range of from 90/10 to 10/90; apart from minor amounts of by-products being present due to side-reactions, the units derived from the polycyclic monomer represented by the general formula (I) have a structure represented by the following general formula (II): wherein l, m, n, p, R1 , R2 , R3 and R4 are
  • a process for the preparation of the above-mentioned random copolymer which comprises copolymerizing ethylene with a polycyclic monomer represented by the above-mentioned general formula (I) in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organic aluminum compound.
  • an optical article comprising a molded body made of the above-mentioned ethylene/polycyclic monomer random copolymer.
  • Figure 1 is an infrared absorption spectrum of a copolymer of the present invention synthesized in Example 1 given hereinafter.
  • the polycyclic monomer of the general formula (I) copolymerized with ethylene apart from minor amounts of by-products being present due to side-reactions has a structure represented by the general formula (II) and, apart from minor amounts which might be present due to ring-opening polymerization, is free from a structure of the following general formula (V): wherein l, m, n, p, R1 , R2 , R3 and R4 are as defined above.
  • the random copolymer of the present invention is chemically stable.
  • Typical examples of the polycyclic monomer of the general formula (I) to be copolymerized with ethylene in the present invention include pentacyclo[10.2.1.1 5,8 .0 2,11 .0 4,9 ]hexadec-6-enes (hereinafter abbreviated as "PCHD compounds”) which are represented by the following general formula [III]: wherein l and n are 0 or 1, R1 , R2 , R3 and R4 , which may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R3 and R4 may together form a ring, and, apart from minor amounts of by-products being present due to side-reactions, the units derived from the polycyclic monomer of this type has a structure represented by the following general formula (IV): wherein l, n R1 , R2 , R3 and R4 are as defined above, and apart from minor amounts which might be present is free from the structure generated by the ring
  • the PCHD compound represented by the general formula (III) can be synthesized, for example, by the Diels-Alder reaction between a tricyclo[6.2.1.0 2,7 ]undec-3-ene (VI) and a cyclopentadiene (VII), which is represented by the following reaction formula: wherein l, n, R1 , R2 , R3 and R4 are as defined above.
  • the cyclopentadiene can be added directly as a monomer to the reaction system.
  • a dicyclopentadiene represented by the following formula (VIII), which is thermally decomposed under reaction conditions to form a cyclopentadiene can be used as the starting compound: wherein l is 0 or 1.
  • the molar ratio of the tricyclo[6.2.1.0 2,7 ]undec-4-ene (VI) to the cyclopentadiene (VII) can be in the range of from 1/1 to 10/1 (if the dicyclopentadiene is used, this molar ratio can be in the range of from 2/1 to 20/1).
  • an increase of this molar ratio causes an increase of the selectivity, conversion and yield, and this tendency is especially prominent at a low temperature. But, if this molar ratio exceeds 5/1 (if the molar ratio exceeds 10/1 when the dicyclopentadiene is used), the conversion and yield are decreased although the selectivity is further increased.
  • the preferred molar ratio is from 2/1 to 5/1 (from 4/1 to 10/1 when the dicyclopentadiene is used).
  • the reaction temperature is preferably 100 to 300°C, more preferably 200 to 250°C.
  • the reaction time depends on the reaction temperature, but the reaction time is preferably 10 minutes to 40 hours, more preferably 30 minutes to 30 hours.
  • the formation of the polymer can be controlled by adding a polymerization inhibitor such as hydroquinone, tertbutylcatechol or p-phenylenediamine.
  • the reaction can be carried out in a medium not inhibiting the reaction, for example, a lower alcohol such as methanol or ethanol, a hydrocarbon such as toluene or cyclohexane, or a halogenated hydrocarbon such as chloroform or tetrachloromethane, and the batchwise method, the semi-batchwise method or the continuous method can be adopted for carrying out the reaction.
  • a medium not inhibiting the reaction for example, a lower alcohol such as methanol or ethanol, a hydrocarbon such as toluene or cyclohexane, or a halogenated hydrocarbon such as chloroform or tetrachloromethane
  • the polycyclic monomers shown in Table 1 can be easily obtained by the Diels-Alder reaction between a pentacyclo[6.6.1 1,8 .1 10,13 .0 2,7 .0 9,14 ]hexadec-4-ene and a cyclopentadiene.
  • the molar ratio of units derived from ethylene to units derived from the polycyclic monomer represented by the general formula (I) is from 10/90 to 90/10, preferably from 20/80 to 80/20.
  • copolymerizable monomers can be further copolymerized with ethylene and the polycyclic monomer represented by the general formula (I), as long as the intended object of the present invention is achieved.
  • copolymerizable monomers of this type there can be mentioned linear and branched ⁇ -olefins having 3 to 10 carbon atoms and cyclo-olefins having 5 to 18 carbon atoms.
  • ⁇ -olefin As specific examples of the ⁇ -olefin, there can be mentioned propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene and 1-decene, but ⁇ -olefins having 3 to 6 carbon atoms are preferred.
  • cyclo-olefin As specific examples of the cyclo-olefin, there can be mentioned cyclopentene cyclohexene, norbornene, methylnorbornene, ethylnorbornene, and 4,7 methano-3a,5,6,7a-tetrahydro-1H-indene.
  • the ethylene/PCHD compound molar ratio is from 10/90 to 90/10 and preferably from 20/80 to 80/20, and the molar ratio of [ ⁇ -olefin and/or cycloolefin]/PCHD compound is not higher than 90/10, preferably from 90/10 to 15/85, and most preferably from 80/20 to 25/75.
  • the other copolymerizable monomer there can be mentioned styrenes such as styrene and ⁇ -methylstyrene, and polyenes such as 1,4-hexadiene.
  • the amount of this copolymerizable monomer is generally smaller than 15 mole% based on the polycyclic monomer.
  • the random copolymer of the present invention can be obtained by copolymerizing ethylene with a polycyclic monomer represented by the general formula (I) and, if necessary, other monomers in a hydrocarbon medium in the presence of a catalyst comprising a hydrocarbon-soluble vanadium compound and a halogen-containing organic aluminum compound.
  • vanadium compound there can be mentioned vanadium halides such as VCl4 and VCl3 , and vanadium compounds represented by the general formula of VO(OR) t X 3-t in which R represents an alkyl group having 1 to 10 carbon atoms, X represents a halogen atom, and t is a number of 0 ⁇ t ⁇ 3.
  • vanadium compound Preferred examples are as follows: VOCl3 , VOBr3 , VO(OCH3)Cl2 , VO(OCH3)2Cl, VO(OCH3)3 , VO(OC2H5)Cl2 , VO(OC2H5) 1.5 Cl 1.5 , VO(OC2H5)2Cl, VO(OC2H5)3 , VO(OC3H7)Cl2 , VO(OC3H7) 1.5 Cl 1.5 , VO(OC3H7)2Cl, VO(OC3H7)3 , VO(O ⁇ n-C4H9)Cl2 , and VO(O ⁇ n-C4H9)2Cl.
  • the halogen-containing organic aluminum compound to be used in combination with the vanadium compound is represented by the general formula of R' u AlX' 3-u in which R′ represents an alkyl group having 1 to 10 carbon atoms, X′ represents a halogen atom, and u is a number of 0 ⁇ u ⁇ 3, preferably 1 ⁇ u ⁇ 2.
  • halogen-containing organic aluminum compound there can be mentioned dimethyl-aluminum chloride, methyl-aluminum dichloride, diethyl-aluminum chloride, ethyl-aluminum sesquichloride, ethyl-aluminum dichloride, di-n-propyl-aluminum chloride, n-propyl-aluminum dichloride, diisobutyl-aluminum chloride and isobutyl-aluminum dichloride.
  • These aluminum compounds can be used alone or in the form of mixtures of two or more thereof.
  • the vanadium compound and the halogen-containing organic aluminum compound are used in amounts such that the Al/V molar ratio is from 1 to 30, preferably from 2 to 20.
  • the copolymerization is carried out in a hydrocarbon medium.
  • a hydrocarbon medium there can be mentioned aliphatic hydrocarbons such as hexane, heptane, octane, decane and kerosine, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane.
  • aliphatic hydrocarbons such as hexane, heptane, octane, decane and kerosine
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • alicyclic hydrocarbons such as cyclohexane.
  • the concentration of the vanadium compound used as the catalyst in the hydrocarbon medium is 0.1 to 30 millimoles per liter and preferably 0.2 to 10 millimoles per liter.
  • the feed ratio between ethylene and the polycyclic monomer represented by the general formula (I) is changed according to the composition of the copolymer, the polymerization temperature and the kind of the solvent, but the ethylene/polycyclic monomer charge ratio is from 1/1 to 1/100 by mole.
  • the ethylene/PCHD compound molar ratio is generally from 1/1 to 1/100, and the ( ⁇ -olefin and/or cyclo-olefin)/PCHD compound molar ratio is not higher than 1/10, preferably from 1/50 to 10/1.
  • the polymerization temperature is generally -60 to 100°C and preferably -30 to 50°C.
  • the polymerization pressure is generally 0 to 50 bar (kg/cm2) and preferably O to 30 bar (kg/cm2).
  • hydrogen can be used for adjusting the molecular weight of the copolymer.
  • the intrinsic viscosity [ ⁇ ] of the copolymer of the present invention is 0.1 to 15 dl/g, preferably 0.5 to 8 dl/g, as determined at 135°C in decalin. To maintain a good balance among the heat resistance, mechanical properties and molding processability, preferably the intrinsic viscosity of the copolymer is within the above-mentioned range.
  • the novel random copolymer of the present invention is usually amorphous or low crystalline, but to manifest an excellent transparency, preferably the random copolymer is amorphous.
  • the crystallinity determined by X-rays is not higher than 5% and is 0% in many cases.
  • a melting point is not observed by differential scanning calorimeter (DSC).
  • the copolymer of the present invention has a high glass transition temperature, and the glass transition temperature is generally 80 to 230°C, more preferably 100 to 200°C. Accordingly, the copolymer of the present invention has an excellent heat resistance.
  • the copolymer obtained by using the polycyclic monomer of the general formula (I), in which p is at least 1, has a higher glass transition temperature than that of the copolymer obtained by using the polycyclic monomer of the general formula (I), in which p is 0, i.e., the PCHD compound represented by the general formula (III), when the comparison is based on the same ethylene content.
  • the copolymer obtained by copolymerizing ethylene with the PCHD compound and the ⁇ -olefin and/or the cyclo-olefin has a higher glass transition temperature than that of the copolymer composed solely of ethylene and the PCHD compound, even if the content of the PCHD compound is reduced. Accordingly, in the copolymer of this type, the amount of the expensive PCHD compound used can be reduced.
  • the novel random copolymer of the present invention can be molded into various shapes by compression molding, extrusion molding injection molding and blow molding customarily adopted for usual synthetic resins.
  • usual additives such as stabilizers against light, heat, oxygen and ozone, flame retardants, plasticizers, lubricants, antistatic agents, fillers, colorants and reinforcers can be incorporated into the copolymer of the present invention according to need.
  • novel random copolymer of the present can be used in combination with various known polymers.
  • polyolefins e.g., homopolymers of ⁇ -olefins such as ethylene, propylene, butene-1, hexene-1 and 4-methylpentene-1 and copolymers of two or more of these ⁇ -olefins
  • styrene polymers e.g., polystyrene, poly- ⁇ -methylstyrene, an acrylonitrile/styrene copolymer and an acrylonitrile/butadiene/styrene copolymer
  • polydienes e.g., polybutadiene and polystyrene
  • polyesters e.g., polyethylene terephthalate and polybutylene terephthalate
  • polyamides e.g., nylon 6, nylon 66, nylon 11 and nylon 12 halogen-containing polymers
  • the ethylene/polycyclic monomer copolymer of the present invention has good optical characteristics such as good transparency and low birefringence, high heat resistance, chemical resistance, mechanical properties, and dimensional stability. Accordingly, the copolymer of the present invention is valuable for use in the manufacture of optical disks such as a digital audio disk, a video disk and a computer disk, optical fibers, plastic lenses and optical filters. Moreover, the copolymer of the present invention can be used for a windowpane of a building or vehicle, and for a medicinal or chemical article such as an injector, a beaker or a graduated cylinder.
  • the compound was identified by the GC-MASS spectrum, 1H-NMR spectrum and 13C-NMR spectrum.
  • a four-neck flask having a capacity of 10 l and equipped with a stirrer, a thermometer, a dropping funnel, and a gas-blowing tube was charged with 5 l of dehydrated toluene after a replacement of the inner atmosphere with nitrogen. Then, 700 g of PCHD and 10 millimoles of VOCl2(OEt) were charged into the flask, and 20 ml of a toluene solution containing 20 millimoles of Et3Al2Cl3 was charged in the dropping funnel.
  • a gaseous mixture of 140 l/hr of ethylene and 400 l/hr of nitrogen was passed through the flask cooled to 10°C by ice water from the gas blowing tube for 15 minutes.
  • Copolymerization was initiated by adding Et3Al2Cl3 dropwise from the dropping funnel, and the copolymerization was conducted at 10°C for 30 minutes. During the copolymerization, the polymerization mixture was kept homogeneous and no precipitation of a copolymer was observed. The copolymerization was stopped by an addition of 60 ml of methanol. The formed copolymer was precipitated by throwing the polymerization liquid into a large quantity of methanol. The formed copolymer was washed with methanol and vacuum-dried at 50°C to obtain 350 g of the copolymer.
  • a press-molded sheet having a thickness of 1 mm was immersed in acetone, ethyl acetate, sulfuric acid (98%) or aqueous ammonia (28%) at room temperature for 20 hours and the change of the appearance was checked. The color or transparency was not changed, and deformation or cracking did not occur.
  • Copolymerization was carried out in the same manner as described in Example 1 except that copolymerization conditions were changed as indicated in Table 2. The results are shown in Table 2 and 3.
  • a four-neck flask having a capacity of 10 l and equipped with a stirrer, a thermometer, a dropping funnel and a gas-blowing tube was charged with 5 l of dehydrated toluene after a replacement of the inner atmosphere with nitrogen. Then, 500 g of PCHD synthesized in the same manner as described in Example 1 and 10 millimoles of VO(OEt)Cl2 were charged into the flask while 20 millimoles of Et3Al2Cl3 was charged in the dropping funnel.
  • a mixed gas of 140 l/hr of ethylene, 180 l/hr of propylene, and 1,000 l/hr of nitrogen was passed through the flask cooled to 10°C by ice water from the gas-blowing tube for 15 minutes.
  • Copolymerization was initiated by adding Et3Al2Cl3 dropwise from the dropping funnel, and the copolymerization was carried out at 10°C for 30 minutes.
  • the polymerization mixture was kept homogeneous and precipitation of a copolymer was not observed.
  • the copolymerization was stopped by an addition of 60 ml of methanol.
  • the formed copolymer was precipitated by throwing the polymerization solution into a large quantity of methanol.
  • the precipitated copolymer was washed with methanol and vacuum-dried at 50°C to obtain 310 g of the copolymer.
  • Copolymerization was carried out in the same manner as described in Example 11 except that copolymerization conditions were changed as shown in Table 5. The results are shown in Table 5 and 6.
  • a four neck flask having a capacity of 10 l and equipped with a stirrer, a thermometer, a dropping funnel and a gas-blowing tube was charged with 5 l of dehydrated toluene after a replacement of the inner atmosphere with nitrogen. Then, 100 g of compound (a) shown in Table 1 and 10 millimoles of VO(OEt)Cl2 were charged into the flask while 20 millimoles of Et3Al2Cl3 was charged into the dropping funnel. A mixed gas of 140 l/hr of ethylene and 1,000 l/hr of nitrogen was passed through the flask cooled to 10°C by ice water for 15 minutes from the gas-blowing tube.
  • Copolymerization was initiated by adding Et3Al2Cl3 dropwise from the dropping funnel, and the copolymerization was carried out at 10°C for 30 minutes. During the copolymerization, the polymerization mixture was kept homogeneous and precipitation of a copolymer did not occur. The copolymerization was stopped by an addition of 60 ml of methanol. The copolymer was precipitated by throwing the polymerization solution into a large quantity of methanol, washed with methanol and vacuum-dried at 50°C to obtain 225 g of the copolymer.
  • the copolymerization was carried out in the same manner as described in Example 22 except that the polycyclic monomer component and copolymerization conditions were changed as shown in Table 7. The results are shown in Tables 7 and 8.
  • PCHD was synthesized in the same manner as described in Example 1, and ethylene was copolymerized with this PCHD in the same manner as described in Example 1 except that the amount charged of PCHD was changed to 500 g and a mixed gas of 140 l/hr of ethylene and 350 l/hr of nitrogen was supplied. As a result, 290 g of a copolymer was obtained.
  • the physical properties of the obtained copolymer were determined in the same manner as described in Example 1.
  • the ethylene content in the copolymer was 55 mole% and the intrinsic viscosity [ ⁇ ] was 1.3.
  • the haze value was 6% and the birefringence was 6 nm.
  • Tm and the glass transition point Tg were measured, it was found that the melting curve was not observed in the range of from -30°C to 400°C and the Tg was 145°C.
  • the flexural modulus was 1.9 x 104 kg/cm2 and the yield strength was 880 kg/cm2.
  • a press-molded sheet having a thickness of 1 mm was immersed in acetone, ethyl acetate, sulfuric acid (98%) or aqueous ammonia (28%) at room temperature for 20 hours, and the change of the appearance was checked. The color or transparency was not changed, and deformation or cracking did not occur.

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Claims (11)

  1. Regelloses Copolymer, das wiederkehrende Einheiten, die von Ethylen abgeleitet sind, und wiederkehrende Einheiten, die von einem durch die folgende allgemeine Formel (I) dargestellten polycyclischen Monomer abgeleitet sind, enthält:
    Figure imgb0026
        worin ℓ, m und n 0 (Null) oder 1 sind, p 0 (Null) oder eine ganze Zahl von mindestens 1 ist, R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellen und R₃ und R₄ zusammen einen Ring bilden können,
    worin
    das molare Verhältnis Ethylen/polycyclisches Monomer der allgemeinen Formel (I) im Bereich von 90/10 bis 10/90 liegt, abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die durch die allgemeine Formel (I) dargestellten, von dem polycyclischen Monomer abgeleiteten Einheiten eine Struktur aufweisen, die durch die folgende allgemeine Formel (II) dargestellt ist:
    Figure imgb0027
        worin ℓ, m, n, p, R₁, R₂, R₃ und R₄ wie oben definiert sind,
    die bei 135°C in Decalin gemessene Grenzviskosität [η] des regellosen Copolymers 0,1 bis 15 dl/g beträgt, und die durch Röntgenstrahlung bestimmte Kristallinität nicht höher als 5% ist.
  2. Regelloses Copolymer gemäß Anspruch 1, worin das polycyclische Monomer ein Pentacyclo[10.2.1.15,8.02,11.04,9]hexadec-6-en ist, das durch die folgende allgemeine Formel (III) dargestellt ist:
    Figure imgb0028
        worin ℓ und n 0 (Null) oder 1 sind, R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellen, und R₃ und R₄ zusammen einen Ring bilden können,
    und,
    abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die von dem polycyclischen Monomer abgeleiteten Einheiten eine Struktur besitzen, die durch folgende allgemeine Formel (IV) dargestellt ist:
    Figure imgb0029
     worin ℓ, n, R₁, R₂, R₃ und R₄ wie oben definiert sind.
  3. Regelloses Copolymer gemäß Anspruch 2, das, abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, aus von Ethylen abgeleiteten, wiederkehrenden Einheiten und wiederkehrenden Einheiten, die von dem durch die allgemeine Formel (III) dargestellten Pentacyclo[10.2.1.15,8.02,11.04,9]hexadec-6-en abgeleitet sind, besteht.
  4. Regelloses Copolymer gemäß einem der Ansprüche 1 und 2, das zusätzlich wiederkehrende Einheiten enthält, die abgeleitet sind von mindestens einem anderen copolymerisierbaren Monomer, das unter α-Olefinen mit 3 bis 10 Kohlenstoffatomen und Cycloolefinen mit 5 bis 18 Kohlenstoffatomen ausgewählt ist.
  5. Regelloses Copolymer gemäß Anspruch 4, das, abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, aus von Ethylen abgeleiteten, wiederkehrenden Einheiten, die von dem durch die allgemeine Formel (III) dargestellten polycyclischen Monomer abgeleitet sind, und wiederkehrenden Einheiten, die abgeleitet sind von mindestens einem Monomer, das ausgewählt ist aus der Gruppe bestehend aus α-Olefinen mit 3 bis 10 Kohlenstoffatomen und Cycloolefinen mit 5 bis 18 Kohlenstoffatomen, besteht, und worin
    das Molverhältnis Ethylen/polycyclisches Monomer der allgemeinen Formel (III) im Bereich von 90/10 bis 10/90 liegt,
    das Molverhältnis des Monomers, das ausgewählt ist aus der Gruppe bestehend aus α-Olefinen und Cycloolefinen, zu dem durch die allgemeine Formel (III) dargestellten polycyclischen Monomer nicht höher als 90/10 ist, und,
    abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die Einheiten, die von dem durch die allgemeine Formel (III) dargestellten polycyclischen Monomer abgeleitet sind, eine durch die allgemeine Formel (IV) dargestellte Struktur besitzen.
  6. Verfahren zur Herstellung eines regellosen Copolymers, das folgende Stufe umfaßt:
    Copolymerisation von Ethylen mit einem durch die allgemeine Formel (I) dargestellten polycyclischen Monomer:
    Figure imgb0030
        worin ℓ, m und n 0 (Null) oder 1 sind, p 0 (Null) oder eine ganze Zahl von mindestens 1 ist, R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, eine Cycloalkylgruppe oder eine ringförmige Arylgruppe darstellen,
    in einem Kohlenwasserstoffmedium in Gegenwart eines Katalysators, der aus einer in Kohlenwasserstoffen löslichen Vanadiumverbindung und einer Halogen enthaltenden organischen Aluminiumverbindung gebildet ist,
    wobei ein regelloses Copolymer gebildet wird,
    in dem
    das Molverhältnis Ethylen/polycyclisches Monomer, das durch die allgemeine Formel (I) dargestellt ist, im Bereich von 90/10 bis 10/90 liegt,
    abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die von dem durch die allgemeine Formel (I) dargestellten Monomer abgeleiteten Einheiten eine durch die folgende allgemeine Formel (II) dargestellte Struktur besitzen:
    Figure imgb0031
        worin ℓ, m, n, p, R₁, R₂, R₃ und R₄ wie oben definiert sind,
    die bei 135°C in Decalin gemessene Grenzviskosität [η] des regellosen Copolymers 0,1 bis 15 dl/g beträgt, und die durch Röntgenstrahlung bestimmte Kristallinität nicht höher als 5% ist.
  7. Verfahren zur Herstellung eines regellosen Copolymers gemäß Anspruch 6, worin das polycyclische Monomer ein durch die folgende allgemeine Formel (III) dargestelltes Pentacyclo[10.2.1.15,8.02,11.04,9]hexadec-6-en ist:
    Figure imgb0032
     worin ℓ und n 0 (Null) oder 1 sind, R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellen, und R₃ und R₄ zusammen einen Ring bilden können,
    und in dem erhaltenen Copolymer, abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die von dem polycyclischen Monomer abgeleiteten Einheiten eine durch die folgende allgemeine Formel (IV) dargestellt Struktur aufweisen:
    Figure imgb0033
        worin ℓ, n, R₁, R₂, R₃ und R₄ wie oben definiert sind.
  8. Verfahren zur Herstellung eines regellosen Copolymers gemäß Anspruch 7, worin ein Monomergemisch, das aus Ethylen und dem Pentacyclo[10.2.1.15,8.02,11.04,9]hexadec-6-en besteht, copolymerisiert wird.
  9. Verfahren zur Herstellung eines regellosen Copolymers gemäß einem der Ansprüche 6 und 7, worin Ethylen mit dem durch die allgemeine Formel (I) oder (III) dargestellten polycyclischen Monomer und mindestens einem Monomer, das ausgewählt ist aus der Gruppe bestehend aus α-Olefinen mit 3 bis 10 Kohlenstoffatomen und Cycloolefinen mit 5 bis 18 Kohlenstoffatomen, copolymerisiert wird, wobei ein Copolymer erhalten wird, in dem
    das molare Verhältnis Ethylen/polycyclisches Monomer, das durch die allgemeine Formel (III) dargestellte ist im Bereich von 90/10 bis 10/90 liegt,
    das molare Verhältnis des Monomers, das ausgewählt ist aus der Gruppe bestehend aus α-Olefinen und Cycloolefinen zu dem durch die allgemeine Formel (III) dargestellten polycyclischen Monomer nicht höher als 90/10 ist, und, abgesehen von geringen Mengen an Nebenprodukten, die bedingt durch Nebenreaktionen vorhanden sind, die von dem polycyclischen Monomer abgeleiteten Einheiten eine durch die allgemeinen Formeln (II) oder (IV) dargestellte Struktur besitzen.
  10. Verfahren zur Herstellung eines regellosen Copolymers gemäß Anspruch 6, worin
    die in Kohlenwasserstoffen lösliche Vanadiumverbindung ausgewählt ist aus der Gruppe bestehend aus VCl₄, VCl₃ und Verbindungen, die durch die Formel VO(OR)tX3-t dargestellt sind, worin R eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, X ein Halogenatom und t eine Zahl von 1 bis 3 ist, die Halogen enthaltende organische Aluminiumverbindung ausgewählt ist aus der Gruppe bestehend aus Verbindungen, die durch die Formel R'uAlX'3-u dargestellt sind, worin R' eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellt, X' ein Halogenatom darstellt und u eine positive Zahl kleiner als 3 ist,
    das Molverhältnis der Vanadiumverbindung zu der organischen Aluminiumverbindung im Bereich von 1 bis 30 liegt, und die Konzentration der Vanadiumverbindung in dem Kohlenwasserstoffmedium 0,1 bis 30 mMol/l beträgt.
  11. Optisches Erzeugnis, das ein aus dem regellosen Copolymer gemäß einem der Ansprüche 1 bis 5 hergestelltes Gehäuse enthält.
EP89118391A 1988-10-06 1989-10-04 Copolymer von Ethylen und ein polycyclisches Monomer, Verfahren zu deren Herstellung und optischer Artikel Expired - Lifetime EP0362814B1 (de)

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US5744664A (en) * 1990-07-05 1998-04-28 Hoechst Aktiengesellschaft Cycloolefin copolymers (COCS) as substrate material for liquid-crystal displays
CA2061003C (en) * 1991-02-12 1999-02-09 Mitsui Chemicals, Inc. Process for isomerizing endo-form of aromatic group-containing norbornenes to exo-form thereof, isomer mixture of aromatic group-containing norbornenes and process for preparing same, and ethylene/aromatic group-contain ng norbornene copolymer and process for preparing same
EP0542488B1 (de) * 1991-11-11 1994-07-06 Mitsui Petrochemical Industries, Ltd. Verfahren zur Herstellung eines statistischen Cycloolefincopolymers
DE4233851A1 (de) * 1992-10-08 1994-04-14 Hoechst Ag Substrat aus zumindest einem Cycloolefin-Copolymer für Aufzeichnungsmedien und Verfahren zu seiner Herstellung
EP0594147A1 (de) * 1992-10-24 1994-04-27 Hoechst Aktiengesellschaft Cycloolefin-Copolymerisate (COC) als Substratmaterial für Flüssigkristalldisplays
WO1995016750A1 (en) * 1993-09-09 1995-06-22 E.I. Du Pont De Nemours And Company Polyamide resin composition and production process
US5323482A (en) * 1993-05-27 1994-06-21 General Electric Company Deuterated organic salts useful in nonlinear optical applications
US5770679A (en) * 1993-12-16 1998-06-23 E. I. Du Pont De Nemours And Company Polyamide resin compositions and production process
EP0692498A1 (de) * 1994-07-13 1996-01-17 Quantum Chemical Corporation Vanadium enthaltender Polymerisationskatalysator
DE19521561A1 (de) * 1995-06-19 1997-01-02 Hoechst Ag Absorptionsmittel
JP3817015B2 (ja) * 1997-04-14 2006-08-30 三井化学株式会社 環状オレフィン系共重合体およびその用途
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